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By Timothy W. Ellis

This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process 'scheme is discussed and a detailed description of ,several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this: method to separate rare earth and other metal based materials will be given.

Jan 1, 1996

By J. L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1991

By A. A. EI-Geassy

High-grade iron ore fines rejected from the DRI plants (>96%Fe2O3) were isothermally reduced in 30-60%CO/H2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either Hz/CO or H2/CO/S mixtures at 823-1 073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduetion mechanism. The influenee of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization rcaction under the different experimental conditions.

Jan 1, 2003

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By R. F. Hammen

Heavy metal contamination of water is a problem of immense national and international proportions. However, effective cleanup is complicated both by the toxicity and the low concentrations of metals in wastewater streams. Using high performance chelation chromatography, the solid phase extraction and purification of extremely dilute metals from water was highly effective. The process is based on selective displacement of metals from a chromatographic column containing a chelating resin. The resin is characterized by extremely efficient adsorption kinetics which allow rapid and complete removal of the metals.

Jan 1, 1993

By J. Fraser Forbes

"The meaning of the term ""process control"" has evolved significantly since its widespread use began in the manufacturing industries in the 1940s. Further, the scope of process control applications has drastically increased both in terms of the breadth of industries using process automation technologies and the vertical integration of these technologies within a single industry. This evolution and integration of process control technologies within the manufacturing industries has proceeded to such an extent that process automation is an integral part of modern business practices.This paper will examine the current status of process control technology from simple process regulation through process performance optimization to business planning. Each layer of the operations automation hierarchy will be discussed both in. terms of the current state-of-the-art and the directions in which these technologies are evolving. The key tools and tasks necessary for success at every level of the automation hierarchy will be introduced. Finally, the critical challenges that must be faced in accomplishing the goal of complete Computer Integrated Manufacturing (CIM) will be described.Finally, although this paper addresses issues of practical importance to any manufacturing company, the discussions will be framed in terms of the particular challenges facing and the opportunities available within the materials manufacturing industries."

Jan 1, 2000

By S. S. Chabot, S. E. James

A recent survey of CEOs from major steel companies worldwide revealed the importance of recycling zinc units from EAF dust, mill scale, blast furnace dust, and other zinc containing streams in their plants. Many processes were developed and installed in response to this challenge. The most successful approach involves the production of a crude zinc oxide and selling it to primary zinc producers to recover the metal value. The problem with this process is the high concentration of halides in the crude oxide. This type of material cannot be processed directly in an electrolytic zinc plant because of corrosion problems it will cause in electrolysis. In 1999, BRZ installed a zinc oxide receiving and washing plant to minimize the impact of halides to its circuit. A description of the washing plant and initial operating results are included.

Jan 1, 2000

By William Petruk, J. H. Gilles Laflamme, Jean Robitaille, Louis J. Cabri

"A quantitative mineralogical study using ore microscopy, electron microscopy, proton-microprobe, image analysis, and material balances was done on samples from the circuit of a concentrator in Quebec, with particular emphasis on the Cu concentrate. The ore contains many different minerals, of which the principal ones, in decreasing order of abundance, are pyrite, sphalerite, chalcopyrite, bornite, galena, tennantite, and pyrrhotite. Minor to trace amounts of covellite, chalcocite, stannoidite, mawsonite, colusite, wittichenite, miharaite, hessite, petzite, electrum, and an unidentified Cu-Pb-Bi-sulfide also occur.Liberation of pyrite is very high in all size fractions for all samples (ranging from 80-91 %). Liberation of chalcopyrite, bomite, sphalerite, and tennantite is relatively high, on average, in the head .sample and Cu concentrate (55-78% and 66-88%, respectively). Most of the chalcopyrite in the flotation tails is not liberated, whereas about one half of the tennantite and sphalerite are liberated in both the flotation and :final tails. Recoveries calculated for the Cu concentrate (on the basis of assays, mineralogy, and image analysis) are chalcopyrite 72. 5%, bornite 73. 7%, sphalerite 41.0%, tennantite 70.9 %, and galena (together with some trace minerals) 34.2%. It was also calculated that the Cu concentrate contains 10.0 % of the pyrrhotite and i.4 % of the pyrite.Materials balance calculations were done on the five major sulfide minerals to determine the mineralogical distribution of 13 major, minor, and trace elements (as determined by protonmicroprobe analyses). It was determined that tennantite is the principal carrier of Bi (67%), As (90%), and Te (86%) in the Cu concentrate. Therefore, removal oftennantite, which is mostly liberated in the Cu concentrate would significantly reduce these three contaminant elements, but at a loss of9% of the Cu, 2.0% of the Zn, and 0.7% of the Ag. The precious metals (Au, Ag) occur as discrete minerals (electrum, petzite, hessite). Some of the Ag also occurs in solid solution in bornite (23.1% of Ag in Cu concentrate), tennantite, and sphalerite. Four of the major sulfides (chalcopyrite, bomite, sphalerite, tennantite) in the ore also contain measurable concentrations of the following trace elements: Se, Cd, In, Sn, and Sb, occurring mostly as solid solutions. Some of these elements are also concentrated (up to about 18%) in minor and trace minerals such as colusite, stannoidite, and mawsonite."

Jan 1, 1999

By R. G. Henley

Mount Isa copper concentrate was combusted in a laminar-flow furnace. The conditions simulated those likely to be encountered in flames in flash smelters of the Outokumpu (air as oxidant) and INCO (oxygen as oxidant) types. The range of conditions studied was as follows: T 400-1400°C, 02 0-100%, SO2 0-95% for residence times up to 0.23 s. The distribution of sulfur, arsenic and lead between the particles and the gas phase was studied. Combustion was very rapid provided the concentrate was adequately dispersed, i.e., no agglomerates. The importance of the latter is discussed. It was possible to oxidize 80% of the sulfur present in the con¬centrate after only 0.1 s reaction time at 1000°C in an atmosphere contain¬ing 8.5% 02 and 12.5% SO2. Best volatilizations (90% of the As, 52% of the Pb) were obtained under localized conditions attained in an air-type flame. Average volatilizations were: air-type flame, As 50%, Pb 32%; oxygen-type flame, As 40%, Pb 30%. The substitution of oxygen for air reduced the arsenic volatilization. The products of combustion were mainly cuprospinel and cuprite; small inclusions of elemental copper were found in some of the particles. At high temperatures, there was a loss of copper due to vaporization of CU( g) CuO kg) (g)

Jan 1, 1983

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By A. K. Kyllo, G. G. Richards

"The formation and control of accretions is an important aspect of process operation for gas injection. The nature of the accretion formed can have a considerable effect on a process, especially on the life of the lance or the refractories in the tuyere region. There are three basic shapes of accretion formed on tuyeres; pipes, hemispheres and hollow-cored hemispheres. However, there are wide variations within these shapes. Generally, the type of accretion formed will depend on the injector design, certain operating parameters and the physical properties of the bath materials. This paper seeks to collect the results of previous and current physical and mathematical modelling together with data gathered from operating furnaces, to obtain a better understanding of the effects of process design and operating variables on accretion formation.IntroductionAn important consideration in the design of a gas injection process is the possible freezing of the bath either around the tuyere or on the lance. With proper design, freezing may be controlled to provide protection of the lance or refractory, and to avoid blockage. Improper design may lead to tuyere blockage and significant refractory or lance erosion. In view of this, a good understanding of the heat transfer in the injection region is essential.While tuyere blockage has been a persistent problem since the inception of submerged gas injection processes, the problem of accretion formation was not studied in detail until the development of the shrouded tuyere by Savard and Lee. A number of studies relating to accretion formation have been carried out since then, but there is still little information available relating the nature of the accretion formed to the design of the injection system.The build up of materials on lances is a similar problem, and may also be either beneficial or detrimental, depending on circumstances. Unfortunately, there is even less information available regarding build up on lances than there is relating to tuyere accretions. While the form of build up on lances is generally a simple coating of the lance, accretions on tuyeres tend to be more complex. Tuyere accretions tend to occur in one of three basic forms: pipe, hemispherical and hollow-cored hemispherical (Figure 1). However, there appears to be a considerable variation within these forms."

Jan 1, 1996

By L. Yin, R. B. Haber, N. Sobh, D. A. Tortorelli, R. W. Hyland Jr.

"We optimize continuous quench process parameters to produce a desired precipitate distribution in aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include a cost function, constraint functions and their sensitivities with respect to the process parameters. These functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine a discrete precipitate particle size distribution. Both the temperature and the precipitate models are solved via the finite element method. Since we use a discrete particle size model, there are as many as 105 degrees-of-freedom per finite element node. After we compute the temperature and precipitate size distributions, we must also compute their sensitivities. This seemingly intractable computational task is resolved by using an element-by-element discontinuous Galerkin finite element formulation and a direct differentiation sensitivity analysis which allows us to perform all of the computations on a PC.1 IntroductionThis work addresses the need for an integrated design capability that links microstructure evolution to the process parameters. It is motivated by the manufacture of lightweight aluminum-alloy extrusions for use in automotive structures. Aluminum alloys offer obvious benefits, however, care must be taken to manufacture favorable microstructures that ensure acceptable structural performance. For example, the manufacturing process for 6000-series components involves hot extrusion of cast aluminum billets followed by either an air or water quench process. The bill~t's initial grain structure is dramatically altered during extrusion by massive mechanical deformations and recrystallization processes. The microstructure continues to evolve during the quench, as complex chemical processes determine the formation of precipitates. The control of the precipit'ate size distribution is vital. Indeed, large precipitates located on grain boundaries serve as crack initiation sites which adversely effect structural crash· worthiness."

Jan 1, 2000

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By Denis Shishin

The pyrometallurgical production and recycling of non-ferrous metals involves the use of complex feed stocks, having awide range of chemical compositions from sources that include mineral sulphide concentrates, high value obsolete materials and process wastes. The commercial viabilities of these operations hinge on the ability to extract value from these materials. Increasingly, modern computer-based tools are used to describe and predict process outcomes, including mass and heat balances, the partitioning of elements and phase equilibria. At the heart of these predictive tools are thermodynamic databases that describe the fundamental chemical properties of a system and all the components present. A comprehensive research program has been established to develop an accurate, self-consistent thermodynamic database describing all gas-slag-matte-metal-speiss-solid phases in the system Cu2O-PbO-ZnO-Al2O3- CaO-MgO-FeO-Fe2O3-SiO2-S-(As-Bi-Sb-Sn-Ag-Au). The database can be used in conjunction with the FactSage computer platform. The accuracy of the database and its application to industrial practice is demonstrated.

By B. Madelin

Over the last ten years, Minemet Recherche and Metaleurop have used an approach in order to investigate and improve the operation of its Smelting furnace and its lead blast furnaces. This approach gives importance- to three complementary means of investigation : - Probing campains in the industrial furnace (temperature and gas analysis profiles), - Chemical and physical modeling (coke combustion, sinter reduction modes, flows patterns, ?.) , - Staged mass and heat balances or kinetic model. This allows to define the limits of operation of each blast furnace and to predict the influence of operating parameters on the furnace performances. For the zinc Imperial smelting furnace, the probing results show the existence- of both an Isothermal reserve zone at 1015ºc and a chemical equilibrium between ZnO and gas which makes possible the use of a practical model for heat and material balances. In particular, very good prediction on the influences of operating parameters can be made. On the contrary, for lead blast furnaces, the probing results show that the thermal and chemical equilibria are not reached. Consequently, classical models for staged heat and mass balances are not sufficient. The use of the other means allows then to characterize the specific influences of operating parameters on the thermal instabilities of these furnaces and their allowed limits.

Jan 1, 1990

By K. J. Murphy, A. R. Smith, A. P. Odorski

"The need for large quantities of oxygen for use in metallurgical processes was a major driving force in the commercialization of tonnage air separation plants. Oxygen, nitrogen and argon impact the quality, energy efficiency and environmental aspects of metals production. Cryogenic air separation processes have been used to supply most industrial requirements, however, newer technologies are available or under development to meet the needs of today's and tomorrow's metallurgical processes. This paper reviews the technical features and state of development of adsorption, chemical, cryogenic and membrane technologies. The technologies are compared in terms of plant size, oxygen purity and pressure, nitrogen and argon co-production, product use pattern and back-up requirements. Computer control systems are described that optimize operation over varying load patterns and ambient conditions; substantially lowering energy consumption. IntroductionOxygen production totalled 390 billion cubic feet in 1987. Although current production is lower than the peak of 455 billion cubic feet reached in 1979, oxygen remains the fifth leading chemical product manufactured in the u.s. (1) Metals manufacturing and fabrication accounts for sixty percent of the oxygen consumed in the u.s. Oxygen use in the steel industry consists of air enrichment for conversion of iron ore, purification of the iron in basic oxygen or other furnaces, and for cutting and welding the finished steel product. Nonferrous ores are smelted in oxygen enriched atmospheres to reduce energy consumption and increase capture of sulfur compounds to meet environmental requirements. In the future oxygen usage is expected to become even more important in metals production as energy costs increase, environmental standards become more stringent, and as new coal based processes become commercialized. Oxygen usage per ton of metal in the new direct reduction processes can be up to ten times higher than traditional steel making."

Jan 1, 1988

By Donna Guillen, Matthew Lehar, Sebastian Freund, Jennifer Jackson, Helge Klockow

"Research and development is currently underway to design an Organic Rankine Cycle (ORC) system with the evaporator placed directly in the hot exhaust stream produced by a gas turbine (GT). ORCs can be used to generate electricity from heat that would otherwise be wasted, thus producing carbon-free energy. In conventional ORC configurations, an intermediate oil loop is used to separate the hot gas from the flammable working fluid. The goal of this research effort is to improve cycle efficiency and cost by eliminating the pumps, heat exchangers and all other added cost and complexity of the additional heat transfer loop by developing an evaporator that resides in the waste heat stream. Direct evaporation – although simpler and less expensive to implement than indirect evaporation of the working fluid – has historically been avoided due to a number of technical challenges imposed by the limitations of the working fluid. The high temperature of the hot exhaust gas may cause decomposition of the organic working fluid and safety is a major concern due to the high flammability of some of these working fluids. The research team has addressed these challenges and developed a new direct evaporator design that can reduce the ORC system cost by up to 15%, enabling the rapid adoption of ORCs for waste heat recovery. The ORC system is intended to integrate with the GT either as a retrofit or to be marketed as a single package, thus maintaining the manufacturer’s warranty.IntroductionWaste heat from turbines and engines used in industrial applications along with waste heat from industrial processes are exceptionally abundant sources of energy. If even a fraction of this waste heat could be economically converted to useful electricity, it would have a tangible and very positive impact on the economic health, energy consumption, and carbon emissions in the U.S. manufacturing sector. Land-based gas turbines are used in a broad range of applications to produce both shaft and electrical power. Most commonly known for generating electricity either as peaking units or as base load units, they are also used to directly drive pumps, compressors or other machinery requiring shaft power. Simple cycle gas turbines have the advantage of a short startup time relative to coal-fired and nuclear units, however, they incur a significant penalty on their efficiency. Large frame gas turbines usually are combined with bottoming steam-based Rankine cycles to increase the overall efficiency of the system and thereby improve their cost performance. Small-frame gas turbines with exhaust temperatures around 500°C could in principle benefit from steam bottoming cycles, but rarely use them in practice because of the high capital cost of the steam system. Particularly for base load small frame gas turbines, akin to those used in pipeline applications, an increase in efficiency is highly desirable."

Jan 1, 2011

By P. N. Anyalebechi

A comparative study of the mechanical properties of automotive steering knuckles produced by three different shape-casting related processes has been conducted. It involved the characterization of the tensile and fatigue properties of aluminum alloy A356 knuckles produced by the vacuum/pressure riserless casting (VRC/PRC), pressure counter pressure casting (PCPC), and the hybrid Cobapress (a casting-forging) processes, in accordance with the appropriate ASTM standards. Surprisingly, the knuckles produced by the hybrid Cobapress process exhibited the lowest strength. For example, the average 0.2% yield strength of the Cobapress knuckles was 31 MPa and 40 MPa less than that of the VRC/PRC and PCPC knuckles, respectively. However, between stresses of 150-200 MPa, the fatigue lives of the VRC/PRC, PCPC, and Cobapress knuckles were comparable. But above 200 MPa, the Cobapress knuckles exhibited the lowest fatigue life. The observed differences in the mechanical properties are attributed to the inherently different microstructures of the different knuckles.

Jan 1, 2009